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NASA NTRS1993

A mechanism for the reduction in risk of decompression sickness in microgravity environment

There is an apparent reduction in the incidence of decompression sickness reported by astronauts (from both the USA and the USSR) during extravehicular activity (EVA). The expected incidence, based on studies conducted under unit gravity conditions in Earth-based laboratories, is greater than that encountered during EVA. A biophysical explanation has been proposed for this difference based upon the mechanism of stress-assisted nucleation. Since the partial pressure ratio at which this gas phase forms is considerably smaller in living systems that in quiescent in vitro models, it was proposed that mechanical forces are involved. In that the lower extremities of astronautics are not gravitationally loaded in microgravity, it is possible that tissue gas micronuclei are but minimally regenerated. Most likely, gas micronuclei formed on Earth (by ambulation under 1 g conditions) would be eventually depleted. In a crossover study, 20 individuals were decompressed--from 1 ATA to 0.43 ATA for 3 hours--following either being fully ambulatory at unit gravity or following being hypokinetic and adynamic (simulated microgravity of 3-day bed rest). The subjects were monitored for gas phase formation by means of precordial Doppler monitoring. The results indicate a reduction in whole body gas phase formation in individuals who were bed rested as compared with themselves when fully ambulatory (p = 0.02). In hypokinetic individuals, the protection conferred was equivalent to an extra 175 minutes of oxygen prebreathe. These results are compatible with a hypothesis relating stress-assisted nucleation to the continual formation of tissue gas micronuclei and their gradual depletion with hypokinesia.

Powell, Michael R.↗

NASA NTRS1994

ROSAT observations of quiescent low mass disk galaxies: No evidence of baryonic blow out

To test the hypothesis that galactic winds associated with star formation in low mass disk galaxies can be an effective means of relocating cold disk gas to a warm tenuous halo, we have obtained long exposure ROSAT Position Sensitive Proportional Counter (PSPC) observations of three such galaxies. The sensitivity of the PSPC to the presence of an extended, approximately 0.15 KEV halo of 10(exp 9) solar mass of gas, is quite high for the exposure times we used. We failed to detect this halo in all three cases and the observed x-ray luminosity of the galaxy is two orders of magnitude less than the hypothetical case in which the mass of gas that has been expelled by previous generations of star formation is equal to the stellar mass of the galaxy itself. This limit is much less than the actual mass of cold gas in these galaxies. Thus, we were unable to verify directly the presence of significant galactic winds in these three galaxies either because they are not operative, because their halos are not sufficiently massive to aid in the retention of this gas, or because the amount of injected gas is just a small percentage of the cold disk gas. If the latter reason is emblematic of low mass galaxies then we would not expect the detection of halos. We also report here the serendipitous detection of Abell 1560, a distance class 7 cluster of unknown redshift.

Bothun, Gregory D.↗

DOE OSTI2019

Characteristics of Wetting-Induced Bacteriophage Blooms in Biological Soil Crust

Biological soil crusts (biocrusts) are photosynthetic “hot spots” in deserts and cover ~12% of the Earth’s terrestrial surface, and yet they face an uncertain future given expected shifts in rainfall events. Laboratory wetting of biocrust communities is known to cause a bloom of Firmicutes which rapidly become dominant community members within 2 days after emerging from a sporulated state. We hypothesized that their bacteriophages (phages) would respond to such a dramatic increase in their host’s abundance. In our experiment, wetting caused Firmicutes to bloom and triggered a significant depletion of cyanobacterial diversity. We used genome-resolved metagenomics to link phage to their hosts and found that the bloom of the genus Bacillus correlated with a dramatic increase in the number of Caudovirales phages targeting these diverse spore-formers ( r = 0.762). After 2 days, we observed dramatic reductions in the relative abundances of Bacillus , while the number of Bacillus phages continued to increase, suggestive of a predator-prey relationship. We found predicted auxiliary metabolic genes (AMGs) associated with sporulation in several Caudovirales genomes, suggesting that phages may influence and even benefit from sporulation dynamics in biocrusts. Prophage elements and CRISPR-Cas repeats in Firmicutes metagenome-assembled genomes (MAGs) provide evidence of recent infection events by phages, which were corroborated by mapping viral contigs to their host MAGs. Combined, these findings suggest that the blooming Firmicutes become primary targets for biocrust Caudovirales phages, consistent with the classical “kill-the-winner” hypothesis. This work forms part of an overarching research theme studying the effects of a changing climate on biological soil crust (biocrust) in the Southwestern United States. To our knowledge, this study was the first to characterize bacteriophages in biocrust and offers a view into the ecology of phages in response to a laboratory wetting experiment. The phages identified here represent lineages of Caudovirales , and we found that the dynamics of their interactions with their Firmicutes hosts explain the collapse of a bacterial bloom that was induced by wetting. Moreover, we show that phages carried host-altering metabolic genes and found evidence of proviral infection and CRISPR-Cas repeats within host genomes. Our results suggest that phages exert controls on population density by lysing dominant bacterial hosts and that they further impact biocrust by acquiring host genes for sporulation. Future research should explore how dominant these phages are in other biocrust communities and quantify how much the control and lysis of blooming populations contributes to nutrient cycling in biocrusts.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS1990

Boundary layer roll circulations during FIRE

The probable mechanism underlying the development of boundary layer roll circulations are studied using wind and temperature profiles measured by the National Center for Atmospheric Research (NCAR) Electra during the stratocumulus phase of the First ISCCP Regional Experiment (FIRE). The expected, or preferred, roll orientations, horizontal wavelengths, and propagation periods are determined by finding the minimum values of the dynamic and thermodynamic forcing parameters, which here are the eddy Reynolds number (Re) and moist Rayleigh number (Ra sub m). These minimum values depend on the height z sub T of the capping temperature inversion and on the values of the Fourier coefficients of the background height-dependent vector wind profile. As input to our nonlinear spectral model, descent and ascent runs by the Electra provide for initial estimates of the inversion height and the wind profiles. In the first phase of the investigation presented here, a mechanism is said to be a probable contributor to the development of roll circulations within the stratocumulus-topped boundary layer if the modeled roll orientation and wavelengths agree with their observed values. Preliminary results using the 14-coefficient model of Haack-Hirschberg (1988) are discussed for the 7 July 1987 Electra Mission 188-A (Flight 5). This mission was flown across a sharp cloud boundary that was within a LANDSAT/SPOT scene. The stratocumulus deck was relatively solid in the eastern part of the scene, while there was a rapid decrease in cloud cover to scattered cumulus clouds aligned in streets to the west. These cloud streets were oriented nearly parallel to the mean wind direction in the layer, which was approximately 340 degrees. The hypothesis that roll circulations occurred in both the relatively clear and the cloudy regions is investigated using as model input a descent profile obtained in the relatively clear air and an ascent profile obtained in the cloudy air. Initial results for the clear air case are that the pure inflection point mode is not possible and the pure thermal mode was oriented 35 degrees to the right of the mean wind direction. The origin of this unacceptably large discrepancy between the observed and modeled results will be investigated further and the conclusions reported at the next FIRE workshop.

Shirer, Hampton N.↗

NASA NTRS1995

Spectroscopy of candidate young globular clusters in NGC 1275

We present spectra of the brightest member of the population of compact blue objects discovered in the peculiar galaxy NGC 1275 by Holtzman et al. (1992) using Hubble Space Telescope images. These spectra show strong Balmer absorption lines like those observed in A-type stars, as expected if the object is a young globular cluster. The age estimated from the strength of the Balmer lines is about 0.5 Gyr, although ages ranging from 0.1 Gyr to 0.9 Gyr cannot be confidently excluded given current models of stellar populations. If these estimated ages are adopted for the young cluster population of NGC 1275 as a whole, the fading predicted by stellar populations models gives a luminosity function which is consistent with that of the Galactic globular cluster system convolved with the observational selection function for the NGC 1275 system. We also use the equivalent widths of the Mg b and Fe 5270 features to constrain the metallicity of the young cluster. Combining these absorption-line widths with the age estimates from the Balmer lines and stellar population models, we find a metallicity of roughly solar, based on the Mg b index, and somewhat higher for the Fe 5270 index. The radial velocity of the absorption lines of the cluster spectrum is offset from the emission lines of the galaxy spectrum at the same position by - 130 km/s, providing further evidence for the identification of the object as a global cluster and opening up the future possibility of studying the kinematics of young cluster systems. The discovery of objects with the characteristics of young globular clusters in NGC 1275, which shows evidence of a recent interaction or merger, supports the hypothesis that galaxy interactions and mergers are favorable sites for the formation of globular clusters.

Zepf, Stephen E.↗

DOE OSTI2022

Dynamics and growth rate implications of ribosomes and mRNAs interaction in E. coli

Understanding how cells grow and adapt under various nutrient conditions is pivotal in the study of biological stoichiometry. Recent studies provide empirical evidence that cells use multiple strategies to maintain an optimal protein production rate under different nutrient conditions. Mathematical models can provide a solid theoretical foundation that can explain experimental observations and generate testable hypotheses to further our understanding of the growth process. In this study, we generalize a modeling framework that centers on the translation process and study its asymptotic behaviors to validate algebraic manipulations involving the steady states. Using experimental results on the growth of E. coli under C-, N-, and P-limited environments, we simulate the expected quantitative measurements to show the feasibility of using the model to explain empirical evidence. Our results support the findings that cells employ multiple strategies to maintain a similar protein production rate across different nutrient limitations. Moreover, we find that the previous study underestimates the significance of certain biological rates, such as the binding rate of ribosomes to mRNA and the transition rate between different ribosomal stages. Furthermore, our simulation shows that the strategies used by cells under C- and P-limitations result in a faster overall growth dynamics than under N-limitation. In conclusion, the general modeling framework provides a valuable platform to study cell growth under different nutrient supply conditions, which also allows straightforward extensions to the coupling of transcription, translation, and energetics to deepen our understanding of the growth process.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS2017

Predicting Cell Death and Mutation Frequency for a Wide Spectrum of LET by Assuming DNA Break Clustering Inside Repair Domains

The high relative biological effectiveness (RBE) of high charged and energy (HZE) particles for cell death, DNA mutations and cancer remain based on experimental data. In this work, we propose that the existence of DNA repair domains is sufficient to predict both cell death and mutation frequencies for any LET by only taking into account experimental data from low-LET, offering one mechanism for RBE across LET. We hypothesize that whenever multiple DNA double-strand breaks (DSBs) are generated within the same DNA repair domain, DSBs are actively regrouped for more efficient repair [1]. This hypothesis has been supported by the low-LET sublinear dose response observed at doses greater than ~1Gy for 53BP1 radiation-induced foci (RIF) reflecting increasing DSB/RIF with dose [2]. Previously, we modeled radiation-induced cell death of human breast cells by first inferring the size of these domains from the dose dependence of low-LET RIF, and by associating a lethality factor to the number of pairs of DSBs in each RIF [1]. In this work, we first integrate the new NASA computer models RITCARD (Relativistic Ion Tracks, Chromosome Aberrations, Repair, and Damage) [3] and BDSTracks (Biological Damage by Stochastic Tracks) for a more accurate microdosimetry and a better model of the nuclear organization to predict the location of DSBs. A large array of particles and energy are simulated, covering more than three orders of magnitude for LET (~1-1000 keV/Âµm). Next, we extend our previous model to predict mutation frequencies by assuming that clustered DSBs increase mutation probability, which is formalized by the mutation frequency being linearly dependent on both the number of DSBs and the number of pairs of DSBs inside individual RIF. Linear coefficients are estimated so that simulations predict accurately mutation frequencies observed in Chinese hamster cells exposed to low-LET. Keeping these coefficients unchanged, we then predict mutation frequencies induced by HZE by simulating DSBs and obtain RBEs for mutations and cell death following the expected experimental bell shape for LET dependence. We also observe an orientation effect that needs to be confirmed, showing different RBE depending on the angle of the HZE beam hitting the main axis of the cell.

Plante, Ianik↗

NASA NTRS2011

Strike-Slip Fault Patterns on Europa: Obliquity or Polar Wander?

Variations in diurnal tidal stress due to Europa's eccentric orbit have been considered as the driver of strike-slip motion along pre-existing faults, but obliquity and physical libration have not been taken into account. The first objective of this work is to examine the effects of obliquity on the predicted global pattern of fault slip directions based on a tidal-tectonic formation model. Our second objective is to test the hypothesis that incorporating obliquity can reconcile theory and observations without requiring polar wander, which was previously invoked to explain the mismatch found between the slip directions of 192 faults on Europa and the global pattern predicted using the eccentricity-only model. We compute predictions for individual, observed faults at their current latitude, longitude, and azimuth with four different tidal models: eccentricity only, eccentricity plus obliquity, eccentricity plus physical libration, and a combination of all three effects. We then determine whether longitude migration, presumably due to non-synchronous rotation, is indicated in observed faults by repeating the comparisons with and without obliquity, this time also allowing longitude translation. We find that a tidal model including an obliquity of 1.2?, along with longitude migration, can predict the slip directions of all observed features in the survey. However, all but four faults can be fit with only 1? of obliquity so the value we find may represent the maximum departure from a lower time-averaged obliquity value. Adding physical libration to the obliquity model improves the accuracy of predictions at the current locations of the faults, but fails to predict the slip directions of six faults and requires additional degrees of freedom. The obliquity model with longitude migration is therefore our preferred model. Although the polar wander interpretation cannot be ruled out from these results alone, the obliquity model accounts for all observations with a value consistent with theoretical expectations and cycloid modeling.

Rhoden, Alyssa Rose↗

NASA NTRS2016

Transgenic Mouse Model for Reducing Oxidative Damage in Bone

Bone loss can occur due to many challenges such age, radiation, microgravity, and Reactive Oxygen Species (ROS) play a critical role in bone resorption by osteoclasts (Bartell et al. 2014). We hypothesize that suppression of excess ROS in skeletal cells, both osteoblasts and osteoclasts, regulates skeletal growth and remodeling. To test our hypothesis, we used transgenic mCAT mice which overexpress the human anti-oxidant catalase gene targeted to the mitochondria, the main site for endogenous ROS production. mCAT mice have a longer life-span than wildtype controls and have been used to study various age-related disorders. To stimulate remodeling, 16 week old mCAT mice or wildtype mice were exposed to treatment (hindlimb-unloading and total body-irradiation) or sham treatment conditions (control). Tissues were harvested 2 weeks later for skeletal analysis (microcomputed tomography), biochemical analysis (gene expression and oxidative damage measurements), and ex vivo bone marrow derived cell culture (osteoblastogenesis and osteoclastogenesis). mCAT mice expressed the transgene and displayed elevated catalase activity in skeletal tissue and marrow-derived osteoblasts and osteoclasts grown ex vivo. In addition, when challenged with treatment, bone tissues from wildtype mice showed elevated levels of malondialdehyde (MDA), indicating oxidative damage) whereas mCAT mice did not. Correlation analysis revealed that increased catalase activity significantly correlated with decreased MDA levels and that increased oxidative damage correlated with decreased percent bone volume (BVTV). In addition, ex-vivo cultured osteoblast colony growth correlated with catalase activity in the osteoblasts. Thus, we showed that these transgenic mice can be used as a model to study the relationship between markers of oxidative damage and skeletal properties. mCAT mice displayed reduced BVTV and trabecular number relative to wildtype mice, as well as increased structural model index in the cancellous tibia. Treatment caused bone loss in wildtype mice, as expected. Treatment also caused deficits in microarchitecture of mCAT mice, although less severe than wildtype mice in some parameters (percent bone volume, structural model index and cortical area). In conclusion, our results indicate that endogenous ROS signaling in both osteoblast and osteoclast lineage cells contributes to skeletal growth and remodeling, and quenching oxidative damage could play a role in bone loss prevention.

transgenic mice↗

DOE OSTI2021

Analysis of Organoiodide Adsorption Mechanisms

If the United States were to engage in the reprocessing of used nuclear fuel, radioactive iodine must be removed from multiple plant off-gas streams to comply with governing regulations. One of these streams is the vessel off-gas (VOG), which arises from the separations process and is expected to contain iodine in primarily organic iodine forms and at parts-per-billion concentrations. The relative lack of knowledge surrounding organic iodine removal from the VOG prompted the US Department of Energy’s Office of Nuclear Energy to initiate experimental efforts targeted at understanding organic iodide removal from prototypic VOG streams. At Oak Ridge National Laboratory (ORNL), this effort has focused on developing a comprehensive understanding of iodine removal from VOG streams by using silver-based sorbents. An important aspect of this testing is developing an understanding of how the sorption of methyl iodide (CH 3 I), the most studied organic iodide species to date, compares with the sorption of other volatile organic iodide species potentially present in the VOG. The work presented here reflects initial testing that will continue to be developed, and final results will be incorporated into an end-of-year report that details a multiyear testing campaign designed to understand iodine mitigation from VOG streams. The goal of these experiments was to determine whether similar reaction pathways govern both CH 3 I and iodobutane (C 4 H 9 I) sorption onto silver mordenite (AgZ), a common silver-based iodine sorbent. More specifically, the authors hypothesized that the sorption of C 4 H 9 I by AgZ will result in the formation of butanol (C 4 H9OH). Effluent monitoring of CH 3 I sorption testing has confirmed methanol production, but analogous monitoring of effluents from C 4 H 9 I sorption studies has not been performed. A series of tests was completed to test this hypothesis with the aim of detecting C 4 H 9 OH downstream of the AgZ bed. Test conditions varied the bed depth, gas stream humidity, and bed temperature post sorption. The effluent gas stream downstream of the AgZ bed was sampled by using gas-tight syringes, and these samples were analyzed by a gas chromatograph coupled to a mass spectrometer. Thin bed C 4 H 9 I tests conducted at -65 and 0°C dew points did not result in C 4 H 9 OH detection in the effluent. This suggests that the sorption mechanism and subsequent reactions could be different from those observed for CH 3 I. The sorption testing continues; additional results will be included in final end-of-year report and will increase the fundamental understanding of organic iodide sorption by AgZ from VOG streams.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

NASA NTRS1988

The effects of feedback lighting on the circadian rhythm of locomotor activity and the reproductive maturation of the male Djungarian hamster (Phodopus sungorus)

The non-parametric model of entrainment suggests that brief pulses of light, delivered between dusk and dawn can simulate the phasing effects of full photoperiods or even constant light (LL). Feedback lighting (LDFB) is a lighting condition where individual animals, otherwise in constant darkness (DD), are exposed to light in response to a monitored behavior. The specific purpose of this type of illumination is to expose the circadian cycle to light only during the subjective night. LDFB has been used to support this hypothesis in several species of nocturnal rodents and one species of diurnal primate by producing similar free-running periods in LDFB as in LL. This lighting condition has also been used to test the hypothesis that exposing the subjective night to even short duration light pulses will maintain reproductive function in long day breeders. In the Syrian hamster (Mesocricetus auratus), however, LDFB is not as photostimulatory as LL despite extensive light exposure during the subjective night. In the experiments presented here, a group of immature male Djungarian hamsters (Phodopus sungorus) were placed in individual light-tight sound attenuated chambers where they had free access to food, water and an activity wheel. The animals were exposed to one of four lighting conditions [DD, LL, LDFB or a neighbor control of feedback lighting (LDFB NC)] for approximately 30 days shortly after weaning. LDFB NC is a lighting condition where a neighbor control hamster receives the identical lighting regime as a paired animal exposing itself to LDFB, yet the neighbor has no control over it. A fifth group was exposed to a light-dark cycle of 16 hours of light and 8 hours of dark (LD16:8). This group was housed in cages in a colony room and did not have access to a running wheel. The free-running periods of the locomotor activity rhythms for hamsters exposed to LDFB and LL were not similar, unlike the results for rats, Syrian hamsters, mice, monkeys and even mature Djungarian hamsters. Immature hamsters exposed to DD and LDFB NC developed more slowly than animals exposed to LL or LD16:8, while hamsters in LDFB developed at an intermediate rate. Thus, it appears that LDFB, although capable of inducing reproductive function in immature Djungarian hamsters, is not as photostimulatory as may have been expected from current photoperiodic models, despite substantial light exposure during the subjective night. Furthermore, this data may suggest that the circadian system of 18-48 day old Djungarian hamsters are still undergoing organizational maturation.

NASA Program Space Biology↗

NASA NTRS2002

Investigation of Venus Surface Properties

Strong localized radar echoes have been observed at decimeter wavelengths from the highlands of Venus since the earliest radar maps were obtained over 30 years ago. These echoes are some five to ten times stronger than those from the presumably basaltic rocks seen at lower altitudes elsewhere on Venus. Observations of thermal emission from the visible disk of Venus at wavelengths corresponding to those used in the radar mapping confirm that the regions of high reflectivity also exhibit low emissivity, as expected from considerations of detailed thermodynamic balance. Two possibilities have been put forward to explain this unexpected aspect of the Venus highlands: 1) surface materials of high effective dielectric constant, probably associated with finite electrical conductivity, and 2) volume scattering associated with multiple scattering from a layer of very-low-loss material containing voids and extending down a few hundred wavelengths beneath the surface. Analogs to these two mechanisms are found elsewhere in the solar system, and each is capable of explaining the basic observations. as of the early 1990's. In 1993, however, it became possible to carry out a bistatic observation of the anomalous highland regions using the Magellan spacecraft, then in orbit about Venus. In this experiment the on-board telemetry transmitter was aimed at the planet's surface with its linear S-band polarization vector oriented at 45 deg to the spacecraft-Venus-Earth scattering plane. The pointing of the transmitting antenna was adjusted so that the spacecraft-to-illuminated-surface incidence angle equalled the Earth-to-Venus-surface incidence angle. In this way, the experiment emphasized the specular scattering component. A full Stokes-Vector analysis of the reflected signal as received on Earth was carried out as the illuminated region scanned across the highland regions of Venus. From the observed position angle of the echo, it was possible to calculate the Fresnel reflectivity of a number of regions on Venus, including the high-altitude Maxwell Montes, and to show unequivocally that the complex dielectric constant of that anomalous area was 100 +/- 50i, as compared to 4.0 (real) for the typical lowland area. Thus this experiment was able to rule out definitively an hypothesis of volume scattering as the explanation for the anomalous scattering in the Venus highlands.

Ford, Peter G.↗

DOE OSTI2026

Affinity and Treatment of LDR Organics in Low Activity Waste by Cementitious Materials – 26109

The physiochemical interactions between organic contaminants, minerals, and polymer additives in grout/cementitious materials are being identified. This research supports a proposed Resource Conservation and Recovery Act (RCRA) treatment variance relevant to the Land Disposal Restriction (LDR) organics present in Hanford tank waste. It provides the technical basis to address the aspects documented by the Environmental Protection Agency in a draft memo necessary to establish that organics can be immobilized/stabilized in a cementitious matrix. The organic species may interact with cementitious minerals, including slag, fly ash, cement, and other components/dopants like activated carbon. A list of 132 reasonably expected LDR organics associated with Hanford tank waste (RPP-RPT-63493, Rev 1a) was screened by functional groups, octanol-water partitioning coefficients, and detection frequency in Hanford tank waste samples. A subset of 15 compounds spanning the identified properties was tested using sorption and leachate tests. These compounds were subjected to traditional batch sorption tests and leaching tests on/from Cast Stone cementitious material with and without activated carbon (a potential organic adsorption additive). The interactions between organic compounds were observed in traditional batch sorption and modified TCLP leachate tests for surrogate Cast Stone material with and without activated carbon addition. Specifically, phthalic acid (negatively charged) and 4-chloroaniline (polar) sorbed strongly to unmodified Cast Stone, while a group of three phenolic compounds (2,4,6-Trichlorophenol, Pentachlorophenol, o-Cresol) sorbed to and were retained by Cast Stone with a 1% activated carbon amendment. Mixtures of these compounds demonstrated visible retention of the organics within the matrix with a quantifiable affinity of the organics to the cement. This novel testing supports the notion that organics within Hanford tank waste would be retained onto the cement phase with the addition of simple materials easily added to the formulation as part of the treatment process. To further provide additional support to this claim, models employing Flory-Huggins theory in conjunction with macromolecular and organic molecule solubility parameters and species activity coefficients are being utilized to better understand these interactions. Within this context, Van Krevelen (VK) and Hansen organic and polymer solubility parameters were used to inform the Flory-Huggins interaction parameter, allowing for a quantifiable method of evaluating polymer-solvent compatibility and, by extension, interactions with proposed binding additives (e.g., activated carbon). These models and measurement should test the hypothesis for our systems understanding and applicability of Flory-Huggins theory, and whether the prediction of organics in the polymer phase versus the aqueous phase can be confidently made using this strategy. The estimation of the organic molecular activity coefficient in these high salt-saturated aqueous systems is another factor that will be assessed. This project aims to predict and understand complicated organic interactions in these heterogenous systems, guiding optimal treatment and stabilization methodologies.

Jolin, Will [Savannah River National Laboratory (S↗

DOE OSTI2023

Tuning Organic Semiconductor Packing and Morphology through Non-equilibrium Solution Processing (Final Report)

Organic semiconductors (OSCs) are a promising candidate to produce low-cost, large area, and flexible electronics. There has previously been successful development of organic field effect transistors (OFETs), photovoltaics (OPV), and bioelectronics using OSCs. Solution processing of these materials allows for the fabrication of large-area devices in the kinetic crystallization regime. The charge transport capabilities have been shown to depend on the morphology and molecular packing of the OSC within thin films. Our hypothesis is that solution processing conditions may significantly impact OSC morphology and as a result the charge transport. Therefore, this work has focused on obtaining a fundamental understanding of the morphology and molecular packing of OSCs for optimal device performance. Through our work, we have gained a better understanding of how these structural conditions were influenced by the solution processing conditions. Our studies have led to a more systematic understanding of the various parameters that impact OSC morphology. Solution processing leads to non-equilibrium films, thus allowing for the formation of diverse morphologies that are inaccessible by other fabrication methods. Previously, our group has focused on tuning the morphology of small-molecular OSCs [53, 55-57]. However, little work had been devoted to polymer OSCs. There was a lack of detailed studies characterizing the solution-state of polymer OSCs in terms of their conformation, degree of entanglement, polymer aggregation, and chain relaxation dynamics. The solution state properties are also likely to be influenced by the rigidity and molecular weight of the polymer OSCs investigated. Thus, we have focused our attention on gaining a better insight of polymer OSC films and solution processing methods. Through this proposal, our approach is to investigate the correlation between solution-state properties and the morphology of the resulting polymer OSC films. We worked three specific aims: investigate the effects of 1) polymer OSC solution-state properties on final film morphology; 2) molecular additives on the solution-state and final film properties; 3) controlled pre-aggregation in the solution-state in the final film morphology. More rigid and planar polymer backbones should promote interchain charge transport and more efficient interchain hopping between polymer chains. Through tailoring the polymer backbone, polymer sidechains, and molecular weight, we expected the altered solution-state properties to affect the final film morphology. In addition, reducing the entanglements and promoting chain alignment will likely prevent charge carrier trapping through conformation disorders. We thus studied different mechanisms, such as molecular additives, to reduce entanglements in solution. Devices fabricated from these solutions were expected to have improved charge transport abilities. In addition to tailoring the solution-state characteristics of the polymer OSCs, we investigated the effect of solution processing methods on the molecular packing and morphology of polymer OSC films. Two main solution processing techniques, e.g., spin-coating and solution shearing, were employed to fabricate OFETs. Spin coating was employed to prepare OSC films, which produce isotropic films. This technique creates several parameters to tune such as spin coating speed, acceleration, and time. Additionally, our research group developed the solution shearing method, which consists of the solution initially sandwiched between two plates. By sliding the top plate, the solution front is exposed and drying begins. This technique allows for the creation of aligned large crystalline domains. Solution shearing consists of different processing parameters which can affect the final morphology, such as shearing speed, substrate temperature and temperature gradient, distance between both plates, and the tilt angle of the top plate. Due to the complexity of the polymer systems investigated, numerous techniques were employed to characterize the polymer OSC solution state and films. All the materials were characterized using the DOE supported synchrotron X-ray scattering facilities at the Stanford Synchrotron Radiation Lightsource (SSRL). Using grazing incidence X-ray scattering (GIXS) and Near Edge X-ray Absorption Fine Structure (NEXAFS) techniques, the crystalline structure and molecular orientations of the thin films were measured. Optical absorption (UV-Vis) spectroscopy was employed to determine the aggregation state in solution and films of the polymer systems. Polarized UV-Vis also allowed for the determination of the relative degree of polymer chain alignment for solution sheared films. Additionally, various other techniques were used to investigate other properties within the film, such as atomic force microscopy (AFM) and solution rheology. Finally, the device performance is quantified through the fabrication and characterization of OFETs, which will highlight the effects of morphology on charge transport.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Preliminary Evidence of Gas-Phase Water Splitting on Holmium Nitrogen Oxide Clusters

Preliminary Evidence of Gas-Phase Water Splitting on Holmium Nitrogen Oxide Clusters Christopher A. Zarzana1, Makayla R. Baxter , Introduction: Molecular hydrogen is a potential energy carrier that could be used to help implement a clean energy economy if it is generated from splitting of water. Improvements in the efficiencies of water-splitting electrolyzers relies on development of novel materials with enhanced performance. However, research in this area is slowed due to underdeveloped understanding of the mechanisms of device performance due to challenges interrogating the fundamental chemical reactions at play in bulk materials. Studies of the intrinsic reactivity of clusters that are representative of the reactive sites of these materials can increase understanding of the fundamental reaction mechanisms involved in hydrogen production, allowing for more efficient development of new water-splitting materials. Methods: Holmium tetranitrato ([Ho(NO3)4]-) clusters were generated in gas-phase using the electrospray ionization source of a Bruker (Billerica, MA, USA) micrOTOF-Q II quadrupole time-of-flight mass spectrometer. Spray solutions consisted of aqueous holmium (Ho) nitrate solutions (at nominally 3 mM) diluted to 30 µM in acetonitrile. The holmium (Ho) tetranitrato clusters were isolated using the quadrupole and were subsequently activated and allowed to react with background water in the collision cell. High resolution, high mass accuracy spectra were recorded using the time-of-flight. Mass accuracy was ensured using external calibration with Agilent (Santa Clara, CA, USA) ESI-L Low Concentration tuning mix. Preliminary data: Collisional activation of the holmium tetranitrato complexes ([Ln(NO3)4]-) resulted in an expected series of ions resulting from the loss of ·NO and ·NO2. This included an ion at m/z = 382.885 assigned as [HoO2(NO3)3]- (theoretical m/z=382.884, error=-1.2 ppm), resulting from loss of ·NO, and an ion at m/z=366.890 assigned as [HoO(NO3)3]- (theorical m/z=366.889, error=-1.8 ppm), resulting from loss of ·NO2. Additional ions were detected that would result from more complicated losses from [Ho(NO3)4]-, including ions at m/z=320.898 assigned as [HoO2(NO3)2]- (theoretical m/z=320.896, error=-4.9 ppm), at m/z=304.904 assigned as [HoO(NO3)2]- (theoretical m/z=304.901, error=-8.1 ppm, very low signal), and at m/z=288.908 assigned as [Ho(NO3)2]- (theoretical m/z=288.907, error=-3.4 ppm). This ion series would arise from loss of some combination of ·NO, ·NO2, and ·NO3, although it is not known whether these losses occur sequentially (e.g. loss of ·NO and ·NO3 to yield [HoO2(NO3)2]-) or as a single species (e.g. direct loss of N2O4). These ions were accompanied by a complementary series representing addition of a single water molecule. This included an ion at m/z=338.908 assigned as [HoO2(NO3)2H2O]- (theoretical m/z=338.907, error=-4.1 ppm), an ion at m/z=322.912 assigned as [HoO(NO3)2H2O]- (theoretical m/z=322.912, error=1.2 ppm), and an ion at m/z=306.918 assigned as [Ho(NO3)2H2O]-, (theoretical m/z=306.918, error=-3.7 ppm). An additional hydrated ion was observed at m/z=276.921 assigned as [HoO2(NO3) H2O]- (theoretical m/z=276.919, error=-7.3 ppm), although corresponding dehydrated ion was not observed. An additional ion was observed at m/z=367.898 that has been assigned as [Ho(NO3)3OH]- (theoretical m/z=367.897, error=-2.5 ppm). It is hypothesized that this ion arises from addition of water to [Ho(NO3)3]- followed by elimination of a hydrogen radical. Neither [Ho(NO3)3]- nor [Ho(NO3)3H2O]- were detected, suggesting that, if the hypothesis is correct, addition of water to [Ho(NO3)3]- and its subsequent splitting is rapid. Elimination of HNO3 from [Ho(NO3)4H2O]- could also yield [Ho(NO3)3OH]-; however, no [Ho(NO3)4H2O]- ions were observed. Novelty: Potential evidence of water splitting on gas-phase lanthanide clusters offers a way to study the intrinsic reactivity of hydrogen-generation materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Numerical Investigation of a Central Fuel Property Hypothesis under Boosted Spark-ignition Conditions

In the present work, a central fuel property hypothesis (CFPH), which states that fuel properties are sufficient to provide an indication of a fuel's performance irrespective of its chemical composition, was numerically investigated In particular, the objective of the study was to determine whether Research Octane Number (RON) and Motor Octane Number (MON), as fuel properties, are sufficient to describe a fuel's knock-limited performance under boosted spark-ignition (SI) conditions within the framework of CFPH. To this end, four TPRF-bioblendstock surrogates having different compositions but matched RON (= 98) and MON (= 90), were first generated using a non-linear regression model based on artificial neural network (ANN). Three unconventional bioblendstocks were included in the analysis: Di-isobutylene (DIB), Isobutanol and Anisole. Skeletal reaction mechanisms were generated for the TPRF-DIB, TPRF-isobutanol and TPRF-anisole blends from a detailed kinetic mechanism. Thereafter, numerical simulations were performed for the fuel surrogates using the skeletal mechanisms and a virtual cooperative fuel research (CFR) engine model, under a representative boosted operating condition. In the computational fluid dynamics (CFD) model, the G-equation approach was employed to track the turbulent flame front and the well-stirred reactor model combined with multi-zone binning strategy was used to capture auto-ignition in the end-gas. In addition, laminar flame speed was tabulated for each blend as a function of pressure, temperature and equivalence ratio a priori, and the lookup tables were used to prescribe laminar flame speed as an input to the G-equation model. Parametric spark timing sweeps were performed for each fuel blend to determine the corresponding knock-limited spark advance (KLSA) and 50% burn point (CA50) at the respective KLSA timing. It was observed that despite same RON, MON and engine operating conditions, the TPRF-Anisole blend exhibited markedly different knock-limited performance from the other three blends. This deviation from the octane index (DI) expectation was shown to be caused by differences in laminar flame speed (LFS). However; it was found that relatively large fuel-specific differences in LFS (> 20%) would have to be present to cause any appreciable deviation from the 01 framework. Otherwise, RON and MON would still be robust enough to predict a fuel's knock-limited performance.

Pal, Pinaki↗

NASA NTRS2005

Deep Interior Mission: Imaging the Interior of Near-Earth Asteroids Using Radio Reflection Tomography

Near-Earth asteroids are important exploration targets since they provide clues to the evolution of the solar system. They are also of interest since they present a clear danger to Earth. Our mission objective is to image the internal structure of two NEOs using radio reflection tomography (RRT) in order to explore the record of asteroid origin and impact evolution, and to test the fundamental hypothesis that some NEOs are rubble piles rather than consolidated bodies. Our mission s RRT technique is analogous to doing a CAT scan of the asteroid from orbit. Closely sampled radar echoes are processed to yield volumetric maps of mechanical and compositional boundaries, and to measure interior material dielectric properties. The RRT instrument is a radar that operates at 5 and 15 MHz with two 30-m (tip-to-tip) dipole antennas that are used in a cross-dipole configuration. The radar transmitter and receiver electronics have heritage from JPL's MARSIS contribution to Mars Express, and the antenna is similar to systems used in IMAGE and LACE missions. The 5-MHz channel is designed to penetrate greater than 1 km of basaltic rock, and 15-MHz penetrates a few hundred meters or more. In addition to RRT volumetric imaging, we use redundant color cameras to explore the surface expressions of unit boundaries, in order to relate interior radar imaging to what is observable from spacecraft imaging and from Earth. The camera also yields stereo color imaging for geology and RRT-related compositional analysis. Gravity and high fidelity geodesy are used to explore how interior structure is expressed in shape, density, mass distribution and spin. Ion thruster propulsion is utilized by Deep Interior to enable tomographic radar mapping of multiple asteroids. Within the Discovery AO scheduling parameters we identify two targets, S-type 1999 ND43 (approximately 500 m diameter) and V-type 3908 Nyx (approximately 1 km), asteroids whose compositions bracket the diversity of solar system materials that we are likely to encounter, from undifferentiated to highly evolved. The 5-15 MHz radar is capable of probing more primitive bodies (e.g. comets or C-types) that may be available given other launch schedules. 5 MHz radar easily penetrates, with the required SNR , greater than 1 km of basalt (a good analog for Nyx). Basalt has a greater loss tangent than expected for most asteroids, although iron-rich M-types are probably not appropriate targets. 15 MHz radar penetrates the outer approximately 100 m of rocky 1 km asteroids and the deep interiors of comets. Laboratory studies of the most common NE0 materials expected (S-, C- and V-type meteorite analogs) will commence in 2005.

Safaeinili, A.↗

NASA NTRS1961

A Study of the Free Oscillations of the Earth

Published observations on the toroidal oscillations of the earth are critically reviewed. A supplementary analysis of the record obtained by the Lamont strain seismometer is presented. Eleven toroidal modes are identified, and it is concluded that the periods are known to within 1 per cent. A perturbation scheme involving the ratio of the angular velocity of the earth to the resonant frequency is used in calculating the effects due to the rotation of the earth on the resonant frequency. The free oscillations are viewed as a superposition of traveling waves. In a nonrotating system two traveling waves combine to produce a stationary standing wave. In a rotating system, the rotation distinguishes between waves that travel in the direction of rotation and those that travel in the opposite direction. Rotation removes a degeneracy and results in a splitting of a spectral peak of order l into 2 times l plus 1 peaks. The fractional displacement in frequency for the lowest-order toroidal oscillations is 1/206 and of the same order as the Q of the peak, so that splitting will probably not be observed in the toroidal oscillations. Viewed locally, rotation causes a particle to precess about a direction parallel to the axis of rotation. This precession will cause a variation of amplitude with time if the motion is recorded by an instrument with an anisotropic response function. Care is therefore needed in studying the time decay of a given spectral peak. Rotation also couples the normal coordinates so that a motion that is initially purely horizontal will develop a vertical component. It is expected that vertical seismometers should record particle motion with the toroidal frequencies. The perturbations of the toroidal oscillations due to core-mantle interaction are treated in detail. An exact expression is obtained for the rate of energy dissipated by a finitely conducting plate oscillating across a magnetic field. The energy dissipated at the core-mantle boundary due to viscous and hydromagnetic coupling is shown to be insignificant as compared with the energy dissipated within the mantle. The toroidal magnetic field leaking into the lower mantle combines with the dipole field, resulting in a stress on the mantle, tending to stiffen the lower boundary. The stress is of sufficient magnitude to produce a displacement toward higher frequency in the lower-order toroidal oscillations. Observations on the (sub 0) T (sub 2) oscillations lead to an estimate of the toroidal magnetic field in the lower mantle. A calculation of elastic energy in the low-order oscillations suggests a value of 10 (sup 18) ergs per cycles per hour for the energy density at low frequencies in the Chilean earthquake. Each mode of oscillation has a characteristic radial distribution of elastic energy associated with it. This distribution determines which parts of the earth contribute most heavily in determining a particular resonant frequency. The distribution of energy for the lower 17 modes for a homogeneous and a Gutenberg model earth is calculated. The resonant frequencies for models of the earth based on the Gutenberg and Lehmann distribution of elastic properties are presented. It is shown that the Gutenberg model earth fits the observations more closely than the Lehmann model and that a slight alteration of the Gutenberg model gives a significantly better fit to the observations. The alteration involves a lower shear-wave velocity in the lower mantle while the Gutenberg velocity distribution is maintained in the upper mantle. Various studies of the earth's oscillations coupled with surface-wave investigations substantiate Gutenberg's hypothesis of a layer of low velocity in the upper mantle. The physical conditions required for the formation of a region of low velocity are examined in detail. The results confirm Birch's earlier statement that a temperature gradient in excess of 6 degrees to 7 degrees per kilometer is needed to produce a decrease in velocity. The low-velocity layer does not require that the temperature approach or exceed the melting temperature. If tile upper mantle is homogeneous, the region of lower velocity should commence at the base of the crust and extend to 150 kilometers under the oceans and about 100 kilometers under continental regions. The distribution of thermal conductivity and radioactivity consistent with the low-velocity layer is also considered.

MacDonald, Gordon J. F.↗